CN102436880A - Thermistor element - Google Patents

Thermistor element Download PDF

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Publication number
CN102436880A
CN102436880A CN201110244422XA CN201110244422A CN102436880A CN 102436880 A CN102436880 A CN 102436880A CN 201110244422X A CN201110244422X A CN 201110244422XA CN 201110244422 A CN201110244422 A CN 201110244422A CN 102436880 A CN102436880 A CN 102436880A
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composition formula
thermal resistor
thermistor
resistor layer
layer
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CN201110244422XA
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CN102436880B (en
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小林宽和
甲昌男
小林将宽
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TDK Corp
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TDK Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/008—Thermistors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
    • G01K7/16—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements
    • G01K7/22—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements the element being a non-linear resistance, e.g. thermistor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/02—Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistors with envelope or housing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K2205/00—Application of thermometers in motors, e.g. of a vehicle
    • G01K2205/04—Application of thermometers in motors, e.g. of a vehicle for measuring exhaust gas temperature

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Thermistors And Varistors (AREA)

Abstract

A highly-reliable thermistor element even when used at a relatively high temperature comprising; element body incorporating two or more internal electrode layers arranging thermistor layer in-between, a pair of terminal electrodes each connected to the mutually faced internal electrode layers and formed on exterior surface of the element body, and lead terminal connected to the terminal electrode, characterized in that the thermistor layer comprises oxide expressed by a composition formula YaCabCrcAldM1eO3 and the thermistor layer substantially does not include Sr or Mn.

Description

Thermistor element
Technical field
The present invention relates to thermistor element, in more detail, relate under and use the thermistor element that high reliability is also arranged than higher temperature.
Background technology
As the thermistor element of the temperature of measuring automobile exhaust gas etc., be main flow always with the thermistor element that can detect 800 ℃ of following temperature.But recently, more and more require, hope that developmental research can measure the thermistor element of 850～1100 ℃ of left and right sides high temperature in the temperature of measuring waste gas etc. more near the place of engine.
For example, patent documentation 1 discloses the electroconductive oxide sintered body that uses with electric conducting material as thermistor, and disclosing yittrium oxide, strontium carbonate, chromium oxide, manganese oxide, aluminium oxide among the embodiment of the document is the electroconductive oxide sintered body of raw material.But, use the thermistor of this electroconductive oxide sintered body, there is the low problem of reliability when under the hot conditions more than 900 ℃, carrying out temperature detection.
[patent documentation 1] TOHKEMY 2003-183075 communique
Summary of the invention
The present invention makes in view of such actual conditions, and its purpose is, is provided at than using the thermistor element that also has high reliability under the higher temperature.
To achieve these goals; Thermistor element of the present invention has the element body of adorning plural interior electrode layer in the thermal resistor layer of clipping, is formed at said element body outer surface; Be connected in each other the pair of terminal electrode of each electrode layer of opposed said interior electrode layer and the lead terminal that is connected in said terminal electrode; It is characterized in that
Said thermal resistor layer has by composition formula Y aCa bCr cAl dM1 eO 3The oxide of expressing,
The relation of a and b is represented by a+b=1 in the said composition formula,
The relation of c, d and e is represented by c+d+e=1 in the said composition formula,
M1 is select among Co, Sn, Nd, Pr, Ga and the Ni at least a in the said composition formula,
A is 0.5≤a≤0.99 in the said composition formula,
B is 0.01≤b≤0.50 in the said composition formula,
C is 0.06≤c≤0.64 in the said composition formula,
D is 0.01≤d≤0.94 in the said composition formula,
E is 0.00≤e≤0.35 in the said composition formula,
Said thermal resistor layer does not comprise Sr and Mn in fact.
The preferably above-mentioned interior electrode layer of above-mentioned thermistor element comprises Pt.
Above-mentioned thermistor element preferably and at least has the partial insulating layer that the said lead terminal of lining is connected in said terminal electrode.
If employing the present invention then can be provided at than using the thermistor element that also has high reliability under the higher temperature.Specifically, use the also little thermistor element of change of the resistance value of before using and use back thermistor element even can provide under hot conditions.
Description of drawings
Fig. 1 be the present invention's one example thermistor element want portion's sectional arrangement drawing.
Fig. 2 is the drawing in side sectional elevation along the thermistor element of II-II line shown in Figure 1.
Symbol description
2 ... Thermistor element (lamination-type thermistor)
4 ... Element body
6,6a ... Thermal resistor layer
8 ... Interior electrode layer
10 ... Terminal electrode
12 ... Lead terminal
14 ... Insulating barrier
16 ... Metal shell
Embodiment
The present invention will be described according to example shown in the drawings below.
Like Fig. 1, shown in 2, the thermistor element 2 of the present invention's one example has element body 4, terminal electrode 10, pair of lead wires terminal 12 and insulating barrier 14.
Each terminal electrode 10 is formed on whole of both ends of the surface of Z-direction of element body 4, but may not be formed on the whole end face.
The front end of pair of lead wires terminal 12 utilizes means such as bonding cream or welding to be connected with each terminal electrode 10.The rear end of each lead terminal 12 is as shown in Figure 2 extends to X-direction.
Again, above-mentioned lead terminal 12 be connected in above-mentioned terminal electrode 10 part at least with insulating barrier 14 linings.
As shown in Figure 2, in the inside of element body 4, interior electrode layer 8 clips thermal resistor layer 6 mutual laminations.In this example, the plane of interior electrode layer 8 be with the parallel plane direction that comprises X axle and Z axle on.An interior electrode layer 8 that clips thermal resistor layer 6 is connected in a terminal electrode 10, and another interior electrode layer 8 is connected in another terminal electrode 10, and the thermal resistor layer 6 that clips with the adjacent interior electrode layer 8 of stack direction (Y axle) constitutes sensor part.
As shown in Figure 2; Interior electrode layer 8 across thermal resistor layer 6 crossing stacks; Be connected to the pair of terminal electrode 10 that forms on the both ends of the surface of Z-direction of element body 4; At the both ends of the stack direction (Y axle) of element body 4, lamination is not as the acting thermal resistor layer 6a of sensor part.
The material of the thermal resistor layer 6 of this example (also comprising thermal resistor layer 6a) is by comprising expression formula Y aCa bCr cAl dM1 eO 3The material of the oxide of expressing constitutes, and has the NTC characteristic.
The relation of a and b is represented by a+b=1 in the above-mentioned composition formula.
The relation of c in the above-mentioned composition formula, d and e is expressed by c+d+e=1.
M1 in the above-mentioned composition formula is select among Co, Sn, Nd, Pr, Ga and the Ni at least a, and that better is Co or Sn.
A in the above-mentioned composition formula is 0.5≤a≤0.99.A in the above-mentioned composition formula takes the numerical value in this scope can access under than higher temperature and uses the thermistor element that also has high reliability.A in the above-mentioned composition formula is advisable with 0.60≤a≤0.99, and 0.70≤a≤0.99 is item better.
B is 0.01≤b≤0.50 in the above-mentioned composition formula.B takes the numerical value in this scope in the above-mentioned composition formula, can access to use under than higher temperature also to have the thermistor element than higher reliability.B is advisable with 0.01≤b≤0.40 in the above-mentioned composition formula, and 0.01≤b≤0.30 is item better.
C is 0.06≤c≤0.64 in the above-mentioned composition formula.C takes the numerical value in this scope in the above-mentioned composition formula, can access under than higher temperature and use the thermistor element that also has high reliability.C is advisable with 0.10≤c≤0.60 in the above-mentioned composition formula, and 0.15≤c≤0.55 is item better.
D is 0.01≤d≤0.94 in the above-mentioned composition formula.D adopts the numerical value in this scope in the above-mentioned composition formula, can access under than higher temperature and use the thermistor element that also has high reliability.D is advisable with 0.10≤d≤0.90 in the above-mentioned composition formula, and 0.25≤d≤0.85 is item better.
E is 0.00≤e≤0.35 in the above-mentioned composition formula.E takes the numerical value in this scope in the above-mentioned composition formula, uses the thermistor element that also has high reliability even then can access under than higher temperature.E is advisable with 0.00≤e≤0.30 in the above-mentioned composition formula, and 0.00≤e≤0.20 is item better.
The thermal resistor layer of this example does not comprise Sr and Mn in fact.In this example, owing to do not comprise Sr, the crystalline texture that can make thermal resistor layer is single-phase, by means of this, can improve the reliability of thermistor element.In this example,, can improve the reliability that thermistor element uses under hot conditions owing to do not comprise Mn again.
Also have, in this example, so-called " not comprising Sr and Mn in fact " means the Sr and the Mn that do not comprise the amount that is higher than the impurity level of can not saying so, if comprise the amount of impurity level then allow.Also have, the impurity level of so-called strontium is meant that the content in the above-mentioned thermal resistor layer is scaled 0.01 mole below the % by element.Again, the impurity level of so-called Mn is meant that the content in the above-mentioned thermal resistor layer is scaled 0.01 mole below the % by element.
Again, the thermistor element of this example, the oxide that its thermal resistor layer is expressed by above-mentioned composition formula constitutes, even therefore in thermal resistor layer, do not comprise also abundant sintering of sintering aid.And owing to also can in thermal resistor layer, not comprise sintering aid, so can improve the reliability of thermistor element.Also have,, can adopt for example SiO as above-mentioned sintering aid 2, Li 2O and B 2O 3Deng.
The not special restriction of the thickness of thermal resistor layer 6 is in this example, preferably about 10～100 μ m.Be stacked on the not special restriction of thickness of the thermal resistor layer 6a in the outside, preferably 40～600 μ m again.
As the conductive material that constitutes interior electrode layer 8; Can adopt for example noble metal and their alloy (Pt-Pd alloy etc.) or base metal and their alloys such as Cu, Ni such as Ag, Pd, Au, Pt; Any formation in the interior electrode layer 8 usefulness Pt of this example, Pt-Pd alloy, Pt-Rh alloy, the Pt-Ir alloy is desirable, adopts Pt then better.
The thickness of interior electrode layer 8 is not special to be limited, and desirable thickness is 0.5～2.0 μ m.
The material of terminal electrode 10 is not special to be limited, and can adopt and the conductive material identical materials that constitutes interior electrode layer 8.
Terminal electrode 10 forms through for example being coated with conductive paste and carrying out sintering processes.The thickness of terminal electrode 10 is not special to be limited, preferably 2～15 μ m.
The section configuration of lead terminal 12 is not special to be limited, and for example, section can be circular, also can be rectangle.Also have, lead terminal 12 uses under the situation of section as the wire rod formation of circle, and the external diameter of wire rod is 200～500 μ m preferably.Again, lead terminal 12 uses under the situation of section as the wire rod formation of rectangle, and the cross dimensions of wire rod is 0.1～0.4mm * 0.2～0.5mm preferably.The material of lead terminal 12 is not special to be limited, and can adopt and terminal electrode 10 identical materials.
Like Fig. 1 and shown in Figure 2, the insulating barrier 14 of ellipsoidal shape be covered with element body 4 around, cover the part that the front end of lead terminal 12 is connected with terminal electrode 10 at least, and the whole week of cladding element main body 4, the rearward end of lead terminal 12 is exposed.
Insulating barrier 14 preferably is made up of the oxide of Al, Mg, Si etc., has the thermal endurance about 1100 ℃.
An example in the face of the manufacturing approach of the thermistor element 2 of this example describes down.The not special restriction of the manufacturing approach of the thermistor element of this example, as long as with known method, illustration adopts the situation of slice method in the explanation below.
At first, prepare finally to become and form interior electrode layer 8 on the surface, form the raw cook (グ リ one Application シ one foretells) of the interior electrode layer cream film of predetermined pattern and the raw cook that does not have interior electrode layer 8.The material that the raw cook utilization constitutes above-mentioned thermal resistor layer forms.Also have, in this material, also can comprise unavoidable impurities such as the following Si of 0.1 weight %, K, Na, Ni.
Then, adopt such material, utilize technique known to make raw cook.Specifically, after evenly mixing, the raw material (for example yittrium oxide, calcium carbonate, chromium oxide, aluminium oxide etc.) that utilizes means such as wet mixed will for example constitute the material of thermal resistor layer makes its drying.
Then calcine (preferably 1000～1200 ℃), the calcining powder is carried out case of wet attrition with the firing condition of suitably selecting.Add bonding agent and organic solvent etc. then in the calcined powder after pulverizing, form slurries, obtain thermal resistor layer cream.Then utilize means such as scraping blade method or stencil printing that above-mentioned thermal resistor layer cream is formed thin slice, make its drying then, obtain raw cook.
Interior electrode layer cream contains above-mentioned various metal.Utilize means such as print process that this interior electrode layer cream is coated on the raw cook, obtain forming the raw cook of the interior electrode layer cream film of predetermined pattern.
Then that these raw cooks are overlapped, pressurization forces together it, with its cut-out, takes out and gives birth to chip after the operation of necessity such as process baking operation.Cutting off cast-cutting saw capable of using instruments such as (Dicing Saw) carries out.
The living chip that takes out burns till (preferably about 1400～1600 ℃) under defined terms, obtain as the element body 4 that burns till body.Then utilize method such as duplicatings be formed on the element body 4 can the formation terminal electrode after burning till terminal electrode cream.As terminal electrode cream, for example can adopting, Pt, Pt/Pd, Pt/Rh, Pt/Ir etc. are the electrode cream of principal component with Pt.Thereafter dry, under the sintering condition of suitably selecting, preferably 1050～1250 ℃ are carried out sintering.
Then, utilize to engage the means such as electrode cream or welding of usefulness, the leading section of lead terminal 12 is bonded on the terminal electrode 10.Under the situation that adopts welding method, utilize resistance welded or arc-welding method etc. to carry out.Under the situation of the electrode cream that adopt to engage usefulness, as material, adopting with Pt, Pt/Pd, Pt/Rh, Pt/Ir etc. is that the joint of principal component is used electrode cream with Pt, and the leading section of lead terminal 12 is engaged in terminal electrode 10.With its oven dry, under suitably selected sintering condition, preferably 1050～1250 ℃, carry out the leading section of lead terminal 12 is sintered in the sintering processes of terminal electrode 10 thereafter.
Then form insulating barrier 14.At first, utilize the ceramic raw material that constitutes above-mentioned insulating barrier 14, utilize known technology to make insulating barrier cream.Specifically, as the material that sets out, weighing Al 2O 3, MgO, SiO 2Deng preparing burden, carry out the wet mixed of stipulated time with ball mill and zirconium pearl.Thereafter with suitably selected baked become condition, preferably 1050～1250 ℃ calcine, the calcining powder is carried out case of wet attrition.Add bonding agent and organic solvent etc. in the calcined powder after pulverizing and form insulating barrier cream.
Utilize methods such as coating or immersion that the insulating barrier cream that obtains is coated on the place of regulation of element body 4 that sintering the leading section of lead terminal 12.Then at suitably selected firing condition, preferably 1050～1250 ℃ of temperature are burnt till, to obtain with the be covered thermistor element 2 of element bodies 4 of insulating barrier 14.
The oxide that the quick resistive element of this example is expressed with above-mentioned composition formula constitutes thermal resistor layer, therefore can be provided at than using the thermistor element that also has high reliability under the higher temperature.Specifically, use the also little thermistor element of resistance change of before using and use back thermistor element even can provide in hot conditions.
Again, in this example, owing to do not contain Sr, the crystalline texture that can make thermal resistor layer is by composition formula Y aCa bCr cAl dM1 eO 3The phase structure of expressing can improve the reliability of thermistor element like this.And in this example, owing to do not contain Mn, the reliability in the time of can improving thermistor element and under hot conditions, use.
The thermal resistor layer of this example contains Cr, but this Cr becomes the surface evaporation of the living chip of element body 4 after burn till when burning till.Therefore on the surface of element body 4, form the defect layer of Cr, form Y 4Al 2O 9, Y 3Al 5O 12, CaCrO 4Etc. out-phase.But the thermistor element of this example is because interior electrode layer 8 clips thermal resistor layer 6 laminations, and the sensor part that therefore influences sensor characteristics is not to be on the surface of element body 4, but is in the inside of element body 4.Therefore,, can not have influence on the sensor part that is present in element body 4 inside yet, can make sensor characteristics keep good even on the surface of element body 4, form out-phase.
And because the unit of the M1 in the composition formula of this example of formation have the effect that hinders sintering, so the baked of element body becomes temperature to want high.Therefore, the more evaporations of Cr when burning till, the out-phase on element body surface forms manyly.But as stated, the thermistor element of this example is owing to form laminated construction, and the out-phase that occurs does not from the teeth outwards influence sensor part.Like this, the thermistor element of this example even contain M1 in the thermal resistor layer, also can make sensor characteristics keep good owing to be laminated construction.
Again, as stated, the element body 4 of this example when burning till Cr from becoming the surface evaporation of the livings chip of element body 4 after baked becomes, so the surface of element body 4 formation loose structure.Therefore, when terminal electrode cream is coated element body 4, or when insulating barrier cream coated element body 4, terminal electrode cream or insulating barrier cream can fit tightly in element body.Consequently, can improve the close property of element body and terminal electrode, improve the close property of element body and insulating barrier simultaneously, improve the reliability of thermistor element.
And the linear expansion coefficient of material and Pt of thermal resistor layer that constitutes this example is more approaching.Therefore, owing to contain Pt,, also be not easy to peel off even simultaneously thermal resistor layer and interior electrode layer are burnt till at interior electrode layer.
Again, when thermistor element at high temperature uses usually, because thermal shock between interior electrode layer and the thermal resistor layer, or can be peeled off between terminal electrode and the thermal resistor layer.But it is more approaching as stated, to constitute material and its linear expansion coefficient of Pt of thermal resistor layer of this example.Therefore; Contain in interior electrode layer or the terminal electrode under the situation of Pt; Even the thermistor element of this example at high temperature uses repeatedly, also be not easy to peel off because of thermal shock causes between interior electrode layer and the thermal resistor layer or between terminal electrode and the thermal resistor layer.Like this, in this example,, can access the high thermistor element of high reliability owing in interior electrode layer or terminal electrode, contain Pt.
Above example of the present invention is illustrated, but the present invention does not receive any restriction of such example, in the scope that does not exceed main idea of the present invention, certainly implement with various forms.
[embodiment]
Enumerate the embodiment that example of the present invention is further specialized below, further the present invention is elaborated.But the present invention just is not defined in these embodiment.
(sample 1～38,41～44)
Thermal resistor layer is with the modulation of cream
As the raw material that constitute thermal resistor layer, prepare yittrium oxide, calcium carbonate, chromium oxide, aluminium oxide, cobalt oxide, tin oxide, neodymia, praseodymium oxide, gallium oxide, nickel oxide, samarium oxide, manganese oxide, strontium carbonate, respectively according to chemical formula Y aCa bCr cAl dM1 eO 3In a, b, c, d and e carry out weighing in the ratio shown in the table 1.The case of wet attrition that these raw materials carried out in ball mill 16 hours is dried then, be made into powder with mortar, newborn rod.Then the powder that obtains is put into the hard alms bowl of aluminium oxide, under 800～1200 ℃ of temperature, carry out 2 hours calcining.
Then, the powder that was sintered into that obtains is used ball mill to pulverize to be micro mist, dewatered drying then, the raw material of the constituent of using as thermistor.
In the present embodiment, use this thermistor to use the constituent raw material, make lamination-type thermistor (lamination sample) and single panel type thermistor (veneer sample) thermistor sample separately.At first the making of lamination-type thermistor is described below.
The making of lamination-type thermistor sample
With the thermistor that obtains with constituent raw material 100 weight portions, polyvinyl butyral resin (Polyvinyl butyral) 10 weight portions, as dioctyl phthalate (DOP) 5 weight portions of plasticizer, mix with ball mill as ethanol 100 weight portions of solvent; Form paste, obtain thermal resistor layer cream.
Utilize the thermal resistor layer cream and the interior electrode layer cream of modulation as stated, be described below and make lamination-type thermistor 2 shown in Figure 1.Also have, the conductive material of interior electrode layer cream adopts Pt in the present embodiment.
At first, the thermal resistor layer cream with obtaining utilizes the scraping blade method on the PET film, to form raw cook.Then on this raw cook, use interior electrode layer cream, utilize screen plate printing method printing internal electrode pattern film, make the raw cook that is printed with the internal electrode pattern film.
Then, outside above-mentioned raw cook, use thermal resistor layer cream separately, utilize the scraping blade manufactured on the PET film, not print the raw cook of internal electrode pattern film.
Then, with the mutual lamination of making as stated of each raw cook, through the laminated body that obtains being carried out the thermal insulation pressurization, make giving birth to chip.
The living chip that then will obtain is cut to the size of regulation, under following condition, takes off bonding agent and handles, burns till and anneal, and obtains element body.
Taking off the bonding agent treatment conditions is,
Programming rate: 30 ℃/hour,
Holding temperature: 300～400 ℃,
Temperature retention time: 8 hours,
Surrounding atmosphere: in the air.
Firing condition is,
Programming rate: 200 ℃/hour,
Holding temperature: 1400～1600 ℃,
Ask during insulation: 2 hours,
Cooling rate: 200 ℃/hour,
Surrounding atmosphere: air.
Annealing conditions is,
Programming rate: 200 ℃/hour,
Holding temperature: 600～800 ℃,
Temperature retention time: 2 hours,
Cooling rate: 200 ℃/hour,
Surrounding atmosphere: air.
Then, the end face of the element body that obtains is carried out abrasive blasting, coating contains the terminal electrode cream of Pt then, obtains the sample of lamination-type thermistor 2 shown in Figure 1.The number of the thermal resistor layer that is clipped by interior electrode layer again, is 3 layers.
The making of single panel type thermistor sample
Thermistor that 100 weight portions obtain with the constituent raw material in, add polyvinyl alcohol 1.5 weight portions (solid content), with mortar, newborn excellent granulation, behind the formation particle, be pressurised into the discoideus formed body of diameter 16mm, thickness 2.5mm.
Then in atmosphere, this formed body carried out 600 ℃, 2 hours heating, takes off after bonding agent handles, in atmosphere, carry out 1400～1600 ℃, 2 hours formally be fired into sintered body.
Then on two faces of the sintered body that obtains, utilize the screen plate printing method printing to contain the cream of Pt,, form electrode, obtain the sample of single panel type thermistor with 1100 ℃ temperature sintering.
According to following order the lamination-type thermistor sample and the single panel type thermistor sample of test piece number (Test pc No.) 1～38 and 41～44 are estimated its resistance change rate respectively.
Resistance change rate
In atmosphere, insulation is 1000 hours under 1100 ℃ of temperature, measures in the atmosphere of insulation before 1000 hours the resistance value (Rs under 1100 ℃ of temperature respectively; Unit: Ω) with the resistance value (Rf of insulation after 1000 hours; Unit: Ω), utilize following formula to ask resistance change rate (Δ R, unit: %).
ΔR＝(|Rs-Rf|)/Rs×100
The mensuration of resistance value is with direct current 4 terminal methods.Again, in the present embodiment, the value of Δ R is that the situation below 5.0% is regarded as well.The result is shown in table 1.
[table 1]
Figure BSA00000562041700131
Can confirm that from sample 1～12 ratio of Y is 0.450＜a＜0.995, preferably 0.5≤a≤0.99; The ratio of Ca is 0.005＜b＜0.550,0.01≤b≤0.50 preferably, and the ratio of Cr is 0.05＜c＜0.650; 0.06≤c≤0.640 preferably; The ratio of Al is 0.01≤d＜0.950,0.01≤d≤0.940 preferably, and the ratio of M1 is the situation (sample 2～5,8～11) of 0.00≤e≤0.35; The situation (sample 1,6,7,12) that is not contained in this scope with the ratio of the ratio of the ratio of the ratio of the ratio of Y, Ca, Cr, Al or M1 is compared, and the resistance change rate of lamination sample is good.
Can confirm that from sample 13～38 and 41～44 even M1 selectes under the situation of Co, Sn, Nd, Pr, Ga, Ni, the ratio of Y is 0.450＜a＜0.995; 0.5≤a≤0.99 preferably, the ratio of C a is 0.005＜b＜0.550, preferably 0.01≤b≤0.50; The ratio of C r is 0.05＜c＜0.650; 0.06≤c≤0.640 preferably, the ratio of Al is 0.01≤d＜0.950, preferably 0.01≤d≤0.940; The ratio of M1 is 0.00≤e＜0.400; 0.00≤e≤0.350 does not preferably comprise in the thermal resistor layer under the situation of Mn or Sr (sample 13～15,17～19,21～23,25～27,29～31,33～35,41～43), is not contained in the situation (sample 16,20,24,28,32,36,44) of this scope with the ratio of M1 or as M1; The situation (sample 37,38) that comprises Mn or Sr is compared, and the resistance change rate of lamination sample is good.
The lamination test agent of test piece number (Test pc No.) 37, owing in thermal resistor layer, comprise Sr, the crystalline texture of thermal resistor layer is except by Y aCa bCr cAl dM1 eO 3Outside the crystalline texture that this composition formula is expressed, be considered to also form for example Y aSr bCr cAl dM1 eO 3The crystalline texture that this composition formula is expressed.And think that consequently, the sensor part of thermal resistor layer does not form single-phase, it is big that resistance change rate becomes.
Can think that the lamination sample of test piece number (Test pc No.) 38 is owing to contain Mn in thermal resistor layer, at high temperature resistance change rate becomes big.
And can confirm from sample 1～38 and 41～44, the thermistor that in veneer sample and lamination sample, comprises in the thermal resistor layer with the identical situation of constituent raw material under, the resistance change rate of lamination sample is better than the resistance change rate of veneer sample.
Each sample of present embodiment is owing to comprise Cr; Cr is from the surface evaporation of the formed body of the living chip of lamination sample or veneer sample; Can think consequently, form the defect layer of Cr on the surface of the element body of the lamination sample of each sample or the sintered body of veneer sample, form Y 4Al 2O 9, Y 3Al 5O 12, CaCrO 4Etc. out-phase.
But the lamination sample is owing to clip thermistor layer laminate interior electrode layer, and the sensor part that therefore sensor characteristics is made a difference is not the surface at element body, but is in inside.Therefore can think that even on the surface of element body, form out-phase, also can not have influence on the sensor part that is present in element body inside, resistance change rate is good.
On the other hand, the veneer sample is owing to form electrode on the surface of sintered body, and sensor part is in the sintered body surface.Therefore can think that the out-phase that is formed at the sintered body surface can have influence on sensor characteristics, compares with the lamination sample, the resistance change rate of veneer sample is higher.

Claims (3)

1. thermistor element; Have the element body of adorning plural interior electrode layer in the thermal resistor layer of clipping, be formed at said element body outer surface; Be connected to pair of terminal electrode on each electrode layer of mutual opposed said interior electrode layer and the lead terminal that is connected in said terminal electrode; It is characterized in that
Said thermal resistor layer has by composition formula Y aCa bCr cAl dM1 eO 3The oxide of expressing,
The relation of a and b is represented by a+b=1 in the said composition formula,
The relation of c, d and e is represented by c+d+e=1 in the said composition formula,
M1 is select among Co, Sn, Nd, Pr, Ga and the Ni at least a in the said composition formula,
A is 0.5≤a≤0.99 in the said composition formula,
B is 0.01≤b≤0.50 in the said composition formula,
C is 0.06≤c≤0.64 in the said composition formula,
D is 0.01≤d≤0.94 in the said composition formula,
E is 0.00≤e≤0.35 in the said composition formula,
Said thermal resistor layer does not comprise Sr and Mn in fact.
2. thermistor element according to claim 1 is characterized in that said internal electrode comprises Pt.
3. thermistor element according to claim 1 and 2 is characterized in that, and has the partial insulating layer that the said lead terminal of lining is connected in said terminal electrode at least.
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